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Title: Formaldehyde roaming dynamics: Comparison of quasi-classical trajectory calculations and experiments

Abstract

The photodissociation dynamics of roaming in formaldehyde are studied by comparing quasi-classical trajectory calculations performed on a new potential energy surface (PES) to new and detailed experimental results detailing the CO + H2 product state distributions and their correlations. The new PES proves to be a significant improvement over the past one, now more than a decade old. The new experiments probe both the CO and H2 products of the formaldehyde dissociation. The experimental and trajectory data offer unprecedented detail about the correlations between internal states of the CO and H2 dissociation products as well as information on how these distributions are different for the roaming and transition-state pathways. The data investigated include, for dissociation on the formaldehyde 2143 band, the speed distributions for individual vibrational/rotational states of the CO products, providing information about the correlated internal energy distributions of the H2 product, and the rotational and vibrational distributions for the CO and H2 products as well as the contributions to each from both the transition state and roaming channels. The agreement between the trajectory and experimental data is quite satisfactory, although minor differences are noted. In conclusion, the general agreement provides support for future use of the experimental techniquesmore » and the new PES in understanding the dynamics of photodissociative processes.« less

Authors:
ORCiD logo [1];  [2];  [3]; ORCiD logo [2]; ORCiD logo [4];  [5]
+ Show Author Affiliations
  1. Georgia Inst. of Technology, Atlanta, GA (United States); Emory Univ., Atlanta, GA (United States)
  2. Emory Univ., Atlanta, GA (United States)
  3. Emory Univ., Atlanta, GA (United States); Univ. of Heidelberg, Heidelberg (Germany)
  4. The Univ. of New South Wales, Sydney, NSW (Australia); The Univ. of Bristol, Bristol (United Kingdom)
  5. The Univ. of New South Wales, Sydney, NSW (Australia)
Publication Date:
Research Org.:
Emory Univ., Atlanta, GA (United States). Dept. of Chemistry and Cherry L. Emerson Center for Scientific Computation
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1465989
Alternate Identifier(s):
OSTI ID: 1361866
Grant/Contract Number:  
FG02-97ER14782
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 147; Journal Issue: 1; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Houston, Paul L., Wang, Xiaohong, Ghosh, Aryya, Bowman, Joel M., Quinn, Mitchell S., and Kable, Scott H. Formaldehyde roaming dynamics: Comparison of quasi-classical trajectory calculations and experiments. United States: N. p., 2017. Web. doi:10.1063/1.4982823.
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Houston, Paul L., Wang, Xiaohong, Ghosh, Aryya, Bowman, Joel M., Quinn, Mitchell S., & Kable, Scott H. Formaldehyde roaming dynamics: Comparison of quasi-classical trajectory calculations and experiments. United States. https://doi.org/10.1063/1.4982823
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Houston, Paul L., Wang, Xiaohong, Ghosh, Aryya, Bowman, Joel M., Quinn, Mitchell S., and Kable, Scott H. Tue . "Formaldehyde roaming dynamics: Comparison of quasi-classical trajectory calculations and experiments". United States. https://doi.org/10.1063/1.4982823. https://www.osti.gov/servlets/purl/1465989.
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@article{osti_1465989,
title = {Formaldehyde roaming dynamics: Comparison of quasi-classical trajectory calculations and experiments},
author = {Houston, Paul L. and Wang, Xiaohong and Ghosh, Aryya and Bowman, Joel M. and Quinn, Mitchell S. and Kable, Scott H.},
abstractNote = {The photodissociation dynamics of roaming in formaldehyde are studied by comparing quasi-classical trajectory calculations performed on a new potential energy surface (PES) to new and detailed experimental results detailing the CO + H2 product state distributions and their correlations. The new PES proves to be a significant improvement over the past one, now more than a decade old. The new experiments probe both the CO and H2 products of the formaldehyde dissociation. The experimental and trajectory data offer unprecedented detail about the correlations between internal states of the CO and H2 dissociation products as well as information on how these distributions are different for the roaming and transition-state pathways. The data investigated include, for dissociation on the formaldehyde 2143 band, the speed distributions for individual vibrational/rotational states of the CO products, providing information about the correlated internal energy distributions of the H2 product, and the rotational and vibrational distributions for the CO and H2 products as well as the contributions to each from both the transition state and roaming channels. The agreement between the trajectory and experimental data is quite satisfactory, although minor differences are noted. In conclusion, the general agreement provides support for future use of the experimental techniques and the new PES in understanding the dynamics of photodissociative processes.},
doi = {10.1063/1.4982823},
journal = {Journal of Chemical Physics},
number = 1,
volume = 147,
place = {United States},
year = {Tue May 16 00:00:00 EDT 2017},
month = {Tue May 16 00:00:00 EDT 2017}
}
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Works referenced in this record:

A novel Gaussian Binning (1GB) analysis of vibrational state distributions in highly excited H2O from reactive quenching of OH* by H2
journal, July 2013

  • Conte, Riccardo; Fu, Bina; Kamarchik, Eugene
  • The Journal of Chemical Physics, Vol. 139, Issue 4
  • DOI: 10.1063/1.4816277

The photodissociation of formaldehyde: A coupled cluster study including connected triple excitations of the transition state barrier height for H 2 CO→H 2 +CO
journal, April 1989

  • Scuseria, Gustavo E.; Schaefer, Henry F.
  • The Journal of Chemical Physics, Vol. 90, Issue 7
  • DOI: 10.1063/1.455821

Photodissociation dynamics of formaldehyde: H 2 ( v , J ) vector correlations
journal, September 1990

  • Carleton, Karen L.; Butenhoff, Thomas J.; Moore, C. Bradley
  • The Journal of Chemical Physics, Vol. 93, Issue 6
  • DOI: 10.1063/1.458777

A Theoretical Study on the Photodissociation of Acetone: Insight into the Slow Intersystem Crossing and Exploration of Nonadiabatic Pathways to the Ground State
journal, May 2010

  • Maeda, Satoshi; Ohno, Koichi; Morokuma, Keiji
  • The Journal of Physical Chemistry Letters, Vol. 1, Issue 12
  • DOI: 10.1021/jz100551y

Roaming Dynamics in Formaldehyde- d 2 Dissociation †
journal, December 2009

  • Goncharov, Vasiliy; Lahankar, Sridhar A.; Farnum, John D.
  • The Journal of Physical Chemistry A, Vol. 113, Issue 52
  • DOI: 10.1021/jp906248j

The Roaming Atom: Straying from the Reaction Path in Formaldehyde Decomposition
journal, November 2004

Direct current slice imaging
journal, April 2003

  • Townsend, Dave; Minitti, Michael P.; Suits, Arthur G.
  • Review of Scientific Instruments, Vol. 74, Issue 4
  • DOI: 10.1063/1.1544053

Evidence of Roaming Dynamics and Multiple Channels for Molecular Elimination in NO 3 Photolysis
journal, July 2010

  • Grubb, Michael P.; Warter, Michelle L.; Suits, Arthur G.
  • The Journal of Physical Chemistry Letters, Vol. 1, Issue 16
  • DOI: 10.1021/jz1008888

Roaming is the dominant mechanism for molecular products in acetaldehyde photodissociation
journal, August 2008

  • Heazlewood, B. R.; Jordan, M. J. T.; Kable, S. H.
  • Proceedings of the National Academy of Sciences, Vol. 105, Issue 35
  • DOI: 10.1073/pnas.0802769105

Two roaming pathways in the photolysis of CH 3 CHO between 328 and 308 nm
journal, January 2014

  • Lee, Kin Long K.; Quinn, Mitchell S.; Maccarone, Alan T.
  • Chem. Sci., Vol. 5, Issue 12
  • DOI: 10.1039/c4sc02266a

Three-State Trajectory Surface Hopping Studies of the Photodissociation Dynamics of Formaldehyde on ab Initio Potential Energy Surfaces
journal, May 2011

  • Fu, Bina; Shepler, Benjamin C.; Bowman, Joel M.
  • Journal of the American Chemical Society, Vol. 133, Issue 20
  • DOI: 10.1021/ja201559r

Permutationally invariant potential energy surfaces in high dimensionality
journal, October 2009

  • Braams, Bastiaan J.; Bowman, Joel M.
  • International Reviews in Physical Chemistry, Vol. 28, Issue 4
  • DOI: 10.1080/01442350903234923

Roaming Radical Pathways for the Decomposition of Alkanes
journal, September 2010

  • Harding, Lawrence B.; Klippenstein, Stephen J.
  • The Journal of Physical Chemistry Letters, Vol. 1, Issue 20
  • DOI: 10.1021/jz101160u

Photodissociation of formaldehyde in a molecular beam
journal, April 1982

  • Ho, Pauline; Bamford, Douglas J.; Buss, Richard J.
  • The Journal of Chemical Physics, Vol. 76, Issue 7
  • DOI: 10.1063/1.443400

Energy dependence of the roaming atom pathway in formaldehyde decomposition
journal, January 2007

  • Lahankar, Sridhar A.; Chambreau, Steven D.; Zhang, Xiubin
  • The Journal of Chemical Physics, Vol. 126, Issue 4
  • DOI: 10.1063/1.2429660

Skirting the transition state, a new paradigm in reaction rate theory
journal, October 2006

Collisionless nonradiative decay rates of single rotational levels of S 1 formaldehyde
journal, June 1979

  • Weisshaar, James C.; Moore, C. Bradley
  • The Journal of Chemical Physics, Vol. 70, Issue 11
  • DOI: 10.1063/1.437354

The molecular dissociation of formaldehyde at medium photoexcitation energies: A quantum chemistry and direct quantum dynamics study
journal, October 2009

  • Araújo, Marta; Lasorne, Benjamin; Magalhães, Alexandre L.
  • The Journal of Chemical Physics, Vol. 131, Issue 14
  • DOI: 10.1063/1.3242082

Photodissociation of acetaldehyde as a second example of the roaming mechanism
journal, October 2006

  • Houston, P. L.; Kable, S. H.
  • Proceedings of the National Academy of Sciences, Vol. 103, Issue 44
  • DOI: 10.1073/pnas.0604441103

Direct Observation of Roaming Radicals in the Thermal Decomposition of Acetaldehyde
journal, January 2010

  • Sivaramakrishnan, R.; Michael, J. V.; Klippenstein, S. J.
  • The Journal of Physical Chemistry A, Vol. 114, Issue 2
  • DOI: 10.1021/jp906918z

Reconstruction of Abel-transformable images: The Gaussian basis-set expansion Abel transform method
journal, July 2002

  • Dribinski, Vladimir; Ossadtchi, Alexei; Mandelshtam, Vladimir A.
  • Review of Scientific Instruments, Vol. 73, Issue 7
  • DOI: 10.1063/1.1482156

Isotopic separation by photopredissociation
journal, August 1972

  • Yeung, Edward S.; Moore, C. Bradley
  • Applied Physics Letters, Vol. 21, Issue 3
  • DOI: 10.1063/1.1654291

Roaming Radical Reactions
journal, February 2011

  • Herath, Nuradhika; Suits, Arthur G.
  • The Journal of Physical Chemistry Letters, Vol. 2, Issue 6
  • DOI: 10.1021/jz101731q

A new (multi-reference configuration interaction) potential energy surface for H 2 CO and preliminary studies of roaming
journal, March 2017

  • Wang, Xiaohong; Houston, Paul L.; Bowman, Joel M.
  • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 375, Issue 2092
  • DOI: 10.1098/rsta.2016.0194

Roaming
journal, April 2014

Permutationally Invariant Polynomial Basis for Molecular Energy Surface Fitting via Monomial Symmetrization
journal, November 2009

  • Xie, Zhen; Bowman, Joel M.
  • Journal of Chemical Theory and Computation, Vol. 6, Issue 1
  • DOI: 10.1021/ct9004917

A novel and facile decay path of Criegee intermediates by intramolecular insertion reactions via roaming transition states
journal, March 2015

  • Nguyen, Trong-Nghia; Putikam, Raghunath; Lin, M. C.
  • The Journal of Chemical Physics, Vol. 142, Issue 12
  • DOI: 10.1063/1.4914987

Roaming Atoms and Radicals: A New Mechanism in Molecular Dissociation
journal, July 2008

  • Suits, Arthur G.
  • Accounts of Chemical Research, Vol. 41, Issue 7
  • DOI: 10.1021/ar8000734

Photodecomposition of CH2O, CD2O, CHDO, and CH2O-CD2O mixtures at xenon flash lamp intensities
journal, March 1969

  • McQuigg, Robert D.; Calvert, Jack G.
  • Journal of the American Chemical Society, Vol. 91, Issue 7
  • DOI: 10.1021/ja01035a002

Thermal Dissociation and Roaming Isomerization of Nitromethane: Experiment and Theory
journal, February 2015

  • Annesley, Christopher J.; Randazzo, John B.; Klippenstein, Stephen J.
  • The Journal of Physical Chemistry A, Vol. 119, Issue 28
  • DOI: 10.1021/acs.jpca.5b01563

Communication: Photodissociation of CH 3 CHO at 308 nm: Observation of H-roaming, CH 3 -roaming, and transition state pathways together along the ground state surface
journal, January 2015

  • Li, Hou-Kuan; Tsai, Po-Yu; Hung, Kai-Chan
  • The Journal of Chemical Physics, Vol. 142, Issue 4
  • DOI: 10.1063/1.4906457

A Global ab Initio Potential Energy Surface for Formaldehyde †
journal, October 2004

  • Zhang, Xiubin; Zou, Shengli; Harding, Lawrence B.
  • The Journal of Physical Chemistry A, Vol. 108, Issue 41
  • DOI: 10.1021/jp048339l

Stereodynamical Origin of Anti-Arrhenius Kinetics: Negative Activation Energy and Roaming for a Four-Atom Reaction
journal, April 2015

  • Coutinho, Nayara D.; Silva, Valter H. C.; de Oliveira, Heibbe C. B.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 9
  • DOI: 10.1021/acs.jpclett.5b00384

Collisionless decay, vibrational relaxation, and intermediate case quenching of S 1 formaldehyde
journal, December 1978

  • Weisshaar, James C.; Baronavski, A. P.; Cabello, A.
  • The Journal of Chemical Physics, Vol. 69, Issue 11
  • DOI: 10.1063/1.436523

Velocity resolved REMPI spectroscopy: a new approach to the study of photodissociation dynamics
journal, January 2009

  • Schmaunz, Andreas; Kensy, Uwe; Slenczka, Alkwin
  • Physical Chemistry Chemical Physics, Vol. 11, Issue 33
  • DOI: 10.1039/b909037a

Roaming dynamics in ion-molecule reactions: Phase space reaction pathways and geometrical interpretation
journal, April 2014

  • Mauguière, Frédéric A. L.; Collins, Peter; Ezra, Gregory S.
  • The Journal of Chemical Physics, Vol. 140, Issue 13
  • DOI: 10.1063/1.4870060

Reaction Products with Internal Energy beyond the Kinematic Limit Result from Trajectories Far from the Minimum Energy Path:  An Example from H + HBr → H 2 + Br
journal, November 2005

  • Pomerantz, Andrew E.; Camden, Jon P.; Chiou, Albert S.
  • Journal of the American Chemical Society, Vol. 127, Issue 47
  • DOI: 10.1021/ja055440a

Experimental and Theoretical Studies of Roaming Dynamics in the Unimolecular Dissociation of CH 3 NO 2 to CH 3 O + NO
journal, July 2013

  • Homayoon, Zahra; Bowman, Joel M.; Dey, Arghya
  • Zeitschrift für Physikalische Chemie
  • DOI: 10.1524/zpch.2013.0409

Roaming as the dominant mechanism for molecular products in the photodissociation of large aliphatic aldehydes
journal, January 2015

  • Tsai, Po-Yu; Li, Hou-Kuan; Kasai, Toshio
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 35
  • DOI: 10.1039/c5cp03408f

Visible/Infrared Dissociation of NO 3 : Roaming in the Dark or Roaming on the Ground?
journal, December 2014

  • Fernando, Ravin; Dey, Arghya; Broderick, Bernadette M.
  • The Journal of Physical Chemistry A, Vol. 119, Issue 28
  • DOI: 10.1021/jp509902d

Slice imaging of the photodissociation of acetaldehyde at 248 nm. Evidence of a roaming mechanism
journal, January 2007

  • Rubio-Lago, L.; Amaral, G. A.; Arregui, A.
  • Physical Chemistry Chemical Physics, Vol. 9, Issue 46
  • DOI: 10.1039/b708310f

Formaldehyde photochemistry: Appearance rate, vibrational relaxation, and energy distribution of the CO product
journal, July 1976

  • Houston, Paul L.; Moore, C. Bradley
  • The Journal of Chemical Physics, Vol. 65, Issue 2
  • DOI: 10.1063/1.433092

The energy dependence of CO(v,J) produced from H2CO via the transition state, roaming, and triple fragmentation channels
journal, July 2017

  • Quinn, Mitchell S.; Andrews, Duncan U.; Nauta, Klaas
  • The Journal of Chemical Physics, Vol. 147, Issue 1
  • DOI: 10.1063/1.4983138

Two‐dimensional imaging of state‐selected photodissociation products detected by multiphoton ionization
journal, July 1987

  • Chandler, David W.; Houston, Paul L.
  • The Journal of Chemical Physics, Vol. 87, Issue 2
  • DOI: 10.1063/1.453276

Velocity map imaging of ions and electrons using electrostatic lenses: Application in photoelectron and photofragment ion imaging of molecular oxygen
journal, September 1997

  • Eppink, André T. J. B.; Parker, David H.
  • Review of Scientific Instruments, Vol. 68, Issue 9
  • DOI: 10.1063/1.1148310

Quasiclassical Trajectory Calculations of Acetaldehyde Dissociation on a Global Potential Energy Surface Indicate Significant Non-transition State Dynamics
journal, August 2007

  • Shepler, Benjamin C.; Braams, Bastiaan J.; Bowman, Joel M.
  • The Journal of Physical Chemistry A, Vol. 111, Issue 34
  • DOI: 10.1021/jp074646q

Roaming Under the Microscope: Trajectory Study of Formaldehyde Dissociation
journal, February 2016

  • Houston, Paul L.; Conte, Riccardo; Bowman, Joel M.
  • The Journal of Physical Chemistry A, Vol. 120, Issue 27
  • DOI: 10.1021/acs.jpca.6b00488

Roaming Radicals
journal, May 2011

Signatures of H2CO Photodissociation from Two Electronic States
journal, March 2006

Evidence for direct molecular oxygen production in CO 2 photodissociation
journal, October 2014

The roaming atom pathway in formaldehyde decomposition
journal, July 2006

  • Lahankar, Sridhar A.; Chambreau, Steven D.; Townsend, Dave
  • The Journal of Chemical Physics, Vol. 125, Issue 4
  • DOI: 10.1063/1.2202241

Roaming Radical Kinetics in the Decomposition of Acetaldehyde
journal, January 2010

  • Harding, Lawrence B.; Georgievskii, Yuri; Klippenstein, Stephen J.
  • The Journal of Physical Chemistry A, Vol. 114, Issue 2
  • DOI: 10.1021/jp906919w

Further aspects of the roaming mechanism in formaldehyde dissociation
journal, May 2008

Roaming reactions: The third way
journal, November 2011

  • Bowman, Joel M.; Suits, Arthur G.
  • Physics Today, Vol. 64, Issue 11
  • DOI: 10.1063/pt.3.1330

Photodissociation dynamics of formaldehyde: H 2 rotational distributions and product quantum state correlations
journal, January 1990

  • Butenhoff, Thomas J.; Carleton, Karen L.; Moore, C. Bradley
  • The Journal of Chemical Physics, Vol. 92, Issue 1
  • DOI: 10.1063/1.458440

Roaming dynamics in radical addition–elimination reactions
journal, June 2014

  • Joalland, Baptiste; Shi, Yuanyuan; Kamasah, Alexander
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5064
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